PL120037B1 - Process for preparing novel 6-ketodecahydroquinolines - Google Patents

Process for preparing novel 6-ketodecahydroquinolines Download PDF

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PL120037B1
PL120037B1 PL1979225532A PL22553279A PL120037B1 PL 120037 B1 PL120037 B1 PL 120037B1 PL 1979225532 A PL1979225532 A PL 1979225532A PL 22553279 A PL22553279 A PL 22553279A PL 120037 B1 PL120037 B1 PL 120037B1
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carbon atoms
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20Oxygen atoms
    • C07D215/22Oxygen atoms attached in position 2 or 4
    • C07D215/227Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20Oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D215/54Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D491/00Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04Ortho-condensed systems

Description

Opis patentowy opublikowano: 25.10.1983 120037 C- i ; l-LNIA Urzedu Patentowego Nitkuj IziczTiupoliiij Ludni) Int. CU C07D 215/20 Twórca wynalazku: Uprawniony z patentu: Eli Lilly and Company, Indianapolis (Stany Zjednoczone Ameryki) Sposób wytwarzania nowych 6-ketodehahydrochinolin Pnzedttniofcem wynalazku jest sposób wytwarza¬ nia nowych 6-ketodekahydrochinoiin o ogólnymi Wzorze 1, w którym R oznacza, girape alkilowa o 1—3 atomach wegla1, grape alkilowa lub grujpe benzylowa a R1 oznacza grupe o wzorze COOZ', gidlzie Z' oznacza grupe alkilowa o 1—&' aitomiach wegla luib grupe alkilowa o 1—(2 atoniach wegla pod/stawiona grupa fenyiowa.Sposób wedlug wynalazku polega na tym, ze zwiazek o ogólnym wzoirze 2, w (którym R i Z' maja wyzej podane znacizenie, poddaje sie reak¬ cji z chlorowodorkiem pitydyny i tjrójiffletókieim chromu. Zwiazki o Wzorze 2. sa nowe.Okreislemie „grapa alkilowa o 1—12 atomach we¬ gla" oznacza grupe metylowa i etylowa a oikreisle- nie „grapa alkilowa o 1—3 atomach wegla" obej¬ muje równiez grupe ptopylowa i izcpiropylowa.Zwiazki o wzorze 1 wytwarza sie postepujac jak przedstawiono na schemacie. Spoisób postepo¬ wania opisano na przykladzie tyfllko pojedynczego steroizomeru (odnosnie steireochemii mostka we¬ glowego) — izomeru 4a^, 8act. Na schemacie Z<— —CO jest acylowa grupa ochronna, gcMe Z o- znacza grupe alkilowa o 1—3 atomach wejgfla, gru¬ pe alkenyiowa o 2-^3 atomach wegla,, grupe alfci- nylowa o 2—J3 atomach wegla, grupe cykloalkilo- wa o 5—6 atomach wegla, grupe fenyiowa lub podisitawicma grupe fenyiowa, przy czym podlsitaw- nlikiem moze byc grupa metylowa, metotasylowa, 10 15 20 25 30 atom chloru i tym poidobnie w dowolnym polo¬ zeniu pierscienia fenylowego. Grape Z—CO moze stanowic, przykladowo, grupa acetylowa, propio- nylowa*, butyrylowa, proctiolilowa, akryilililowa, benzoilowa, p-tolksilowia, o^chloirobenzoilowa, m- -nietokisymlbenzodiowia i tym podobne.Zgodnie zie schematem, 4^acyloikByHcyMoheksa- non o wzorze 3 poddaje sie reakcji z asitrem a- -chlorowcometyloakrylanowym, przykladowo estrem etylowym i amina o wzorze RNH2, gdzie R ozna¬ cza g*rape alkilowa o 1^3 atomach wegla, girupe allilowa lub grupe benzylowa.Produktem tej reakcji jest mttesza(nina DL-1- ^dlstawionej-3-eitolksykar^ 5,6,7,8-ofctahydlrochinoliny i DL-il-podstawionej-HA 3,4,'4a,5^97-ok1ahydlrochlinoliny o wzorze 4, w kltó- rym kropkowana' linia oznacza alternatywne po¬ lozenie podwójnych wiazan. Otrzymane izomery przeksztalca- sie w sole chlorowodorkowe a ich mieszanine redlukuje sie cyjanoborowodorkiem so¬ dowym otrzymujac trans-DL-l^podisitawlona-B-eito- ksykanbonylo^6iacyloksydekahydlrochinoline o wzo¬ rze 5.. W wyniku hydrolizy tego dwueistnu otrzymuje sie kwas 6nhyidlroklsyr3-Jkarfooksylowy a nastepnie przez reetstryfikacje kwasowej grupy karboksylo¬ wej etanolem otrzymuje sie tranis-iDL-il-poidlstawiona-SHetoiksy- karbonylo-6-hydlroiklsyH^kahydliochkioline o wzorze 120 037120 037 3 4 sadlke ekstrakcyjna Soxleta wypelniona sitami molekularnymi typu 3A. Mieszanine reaikcyljna o- chlodizono, rozcienczono wodnym roztworom wo¬ doroweglLaiiu sodowego i alkaliczna mieszanine 5 ekstrahowano kilkakrotnie chloroformem. Eks¬ trakty chloroformowe polaczono i przemyto nasy¬ conym wodnymi roztworem chlorku sodu i suszo¬ no. Po oid|pedizeniu chlorotformiu otrzymano 10,3 g pozostalosci zawierajacej trans 10 toksyfearbonylo^-hydirolksydekianydrochinolme wy¬ tworzona w powyzszej hydrolizie po chromatografii na 150 g preparatu florisil z uzycieim chlorofor¬ mu zawierajacego zwiekszajace sie (£—10!%) ilosci metanolu jako eluenta. 15 Przygotowano rozitwor z 8,8 g transHDL-\l-(pto- pylo-B-e;to(ksyikarbonydo-6-hydlroiksyicyekahyidlrochi- noliny i 4O0 ml dwuchloirometylaniu i podano don 4,1 g octanu sodowego. Nastepnie dodano 10,8 g odczynnika chlorowodorek pirydyny, trójtlenek 20 chromu i otrzymana mlieszanine mieszano w ciagu okolo 22 godzin, po czym przesaczono i przesacz zatezono pod piróznia. Oitrzymany koncentrat roz¬ puszczono w chloroformie a roztwór chloroformo- wy poddano chromatografii na 150 g preparatu florisil z. uzyciem chloroformu zawierajacego zwiejkszajace sie .(1—12%) iloisici metanolu jako e- luenta. Metoda chromatografii ciemkowarstwowej stwierdzono, ze frakcje zawieraja trans-DL-il-pro- pylo-S-etoksyikairtoonylo-G-lketoideikahydrochinoline.Charakterystyka produktu /Izwiiazek trans o, wzo¬ rze 1, w którym R=n^CaH7 a R1=COOC2H5/ Widmo IR/CHay 1715 -cm-1 keton C=0 17i25 cm-1 ester G=0 Widdno NMR '/GOdJ /\W JYEHz/ . 53 cykle/s, triplet, N^CH2^CH2—CH3 77 cykli/ls, triplet, —O—CH2—CH3 250 cykli/s, kwartet, —O^CH2—-CH3 2. Utleniajac grupe hydroksylowa odczynnikiem • Saretta (chlorowodorek pirydyny i trójltlenek chromoi) otrzymuje sie odpowiedni nowy 6-keto zwliazelk o Wzorze 1.Zwiazki o wzorze 1 stanowia produkty posred¬ nie do wytwarzania nowych oktanydropirazolo[3,4- ig]chinolin, .które isa przydatne jaJko srodki lecz¬ nicze o dzialaniu agonistycznyrn wzgledem dopa- miny.Przyikilatd Mieszanine 10 ml propyloamfiny i 400 ml toluenu ochlodzono w mieszaninie wody z liodieni. Dodano do niej po kropli roztwór 16,5 g a-^bromometyloi/aikrylanu etylu..Otrzymana imlieszanine mieszano i chlodzono w ciagu okolo 25 mliniut. Nafstejpnie do.dlano po- kropli roztwór 11 g 4-lhenzoilloksycyklo-ihe'ksanonu w 75 ml toluenu. Te nowa mlieszanine ogtrzewano w temperaturze wrzenia pod chloidnica zwrotna w atmosferze azotu w ciagiu 213 godzin. Chlodnice zwrotna wyposazono w nasadke ekstrakcyjna Soxleta wypelniona sitami molekularnymi typu 5A w celu usuniecia wody. ¦Naistejpinlie mieszanine reakcyjna oichlodzono i przesaczono. W pozosta¬ losci {po odpedzaniu rozpuszczalników znajdowaly sie l-propylo-3-etoiklsyika^bonylo-6-lbenzoilolksy^l,2, 3,4,5,6,7,8K)k)tahydTochmolina ora-z .l-pa:opylo-3^eto- klsyikairibonylo-6-ibenzoiloiksy-il,2(^3,4,4a,i5,6,,7-olktahy- drochinolina.Pozostalosc te rozpuszczono w mieszaninie eter— chloroform i otrzymany rozfe^ór... nasycono gazo¬ wym chlorowodorem przy jednoczesnym utrzymy¬ waniu temperatury reakcji w granicach 0—5°C.Rozpuszczalnik zdekanltowano znaid krysztalów chlorowodorków tak otrzymanych. Ohlorowodbirlkji rozpuszczono w 100 ml metanolu, dodano 300 ml THF i koncowy rozitfwóirocliiojdlzono w mieszani¬ nie wody z lodem. Podczas miLeseania i ochladza¬ nia dodano nastepnie porcjami 15.sg wodoir'ku sodowego, po.czyim miesaanane reaikcyj^ na mieszano ptzez dalsze ly2l5 £odlzftny i rozcien^ czono nastepnie woidlnym roztworem weglanu so¬ dowego. , •.. .Wodina alkaliczna mieszanine eksibrajaowano da^ lej kilkakrotnie octanem etylu, ekstrakty poiaczo-.. no i przemyto nasyconym . wodnym < roztworem chlorku sodu i suszono. Po odpedzeniu rozpusz- czalniika otrzymano trans-DLnl^ropylo-G^01^ lrarbonylor^-lbenizoilofesy^ Zwiazek ten trozpmszic^ono w m&eszan^nje 400.,ml metanolu i 100 ml 2N wodoejgo rozporu wodo¬ rotlenku sodowego, mieszano -w temtperat^i^zie .po¬ kojowej w atmosferze azotu w ,. c iajgia -6^4 godzin i po tym czasie lotne substancje usunieto .przez oidjparowanie pod próznia., .Otrzymana, pozostalosc rozproszono w 800 ml etanole i li5 ml 1 2N wodL nego roztworu kwasu, sokiego. ; : Mieszanine estryfikacyjna ogrzewano w tempe¬ raturze wrzenjia pod chlodnica. zawrotna i odde¬ stylowano- okolo 300 ml rozpuszczalnika. Dodano nastepnie dalsze 300 ml etanofllu i mieszanine re- aikcyjna ogrzewano w temperaturze wrzenia w ciagu 26 godlzin w aparaturze wyposazonej w na- PL PLThe patent was published: October 25, 1983 120037 C- i; I-LNIA of the Patent Office Nitkuj IziczTiupoliiij Ludni) Int. CU C07D 215/20 Inventor: Authorized by the patent: Eli Lilly and Company, Indianapolis (United States of America). ketodecahydroquinoneines of the general Formula 1, wherein R is an alkyl group of 1-3 carbon atoms, an alkyl group or a benzyl group, and R1 is a COOZ 'group, and Z' is an alkyl group of 1— & 'carbon aithomy, or an alkyl group The method according to the invention consists in the fact that a compound of the general formula 2, in which R and Z 'have the above-mentioned characterization, is reacted with pithidine hydrochloride and chromium tribrachate The compounds of Formula 2 are new. The term "1-12 carbon alkyl group" denotes a methyl and ethyl group, and an "alkyl group of 1-3 carbon atoms" also includes a ptopyl group and an isopyropyl group. a. Compounds of formula I are prepared following the scheme. The procedure is described by way of example only of a single steroisomer (referring to the carbon bridge steireochemistry) of the 4α, 8act isomer. In the scheme, Z <- —CO is an acyl protecting group, gcMe Z is an alkyl group with 1 to 3 carbon atoms, an alkenyl group with 2 to 3 carbon atoms, an alphinyl group with 2 to 3 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, a phenyl group or a sublimation of a phenyl group, the sublimation of which may be a methyl group, a methotasyl group, a chlorine atom and the like at any position in the phenyl ring. Grape Z — CO can be, for example, an acetyl, propionyl *, butyryl, procthiolyl, acryloylyl, benzoyl, p-tolxyl, o-chloirobenzoyl, m-naphthoxy-benzoyl group, and the like. 3 is reacted with an α-halomethyl acrylate asiter, for example an ethyl ester, and an amine of the formula RNH 2, where R is a 1-3 carbon g-rape alkyl group, an allyl group or a benzyl group. The product of this reaction is mttesha ( nine DL-1- ^ d-substituted-3-eitolxycar ^ 5,6,7,8-ofctahydlroquinoline and DL-yl-substituted-HA 3,4, '4a, 5 ^ 97-oxyhydroquinoline of formula 4, in dotted dotted The line represents the alternative position of the double bonds. The resulting isomers are converted into hydrochloride salts and their mixture is redluxed with sodium cyanoborohydride to give trans-DL-1-sisitavalone-B-eitoxycanbonyl, 6-acyloxydecahydlroquinoline 5 of the formula The acid 6 is obtained by hydrolysis of this bivalve Nhyidlroclsyr-3-carboxylic acid and then by re-esterification of the acidic carboxyl group with ethanol, the tranis-iDL-yl-substituted-SHetooxy-carbonyl-6-hydroixyloxy-hydroxyl of the formula 120 037120 037 3 4 molecular extracts of the 3-hydroxy type is obtained. The reaction mixture was cooled, diluted with aqueous sodium hydrogen carbonate solutions, and the alkaline mixture was extracted several times with chloroform. The chloroform extracts were combined and washed with a saturated aqueous sodium chloride solution and dried. After the use of chlorotforming, 10.3 g of a residue containing the trans-toxichydrolxydecanethoquinolme obtained in the above hydrolysis after chromatography were obtained on 150 g of florisil with the use of chlorophore containing increasing (£ -10%) of the eluent of methanol as eluent. . A solution was prepared with 8.8 g of transHDL- 1- (ptopyl-B-e; to (xicarbonyl-6-hydroixicekahyidl-quinoline and 4O0 ml of dichloromethylate) and dosed with 4.1 g of sodium acetate. Then 10.8 g of the reagent was added. Pyridine hydrochloride, chromium trioxide and the resulting mixture were stirred for about 22 hours, then filtered and the filtrate was concentrated under a pyrotechnic chamber. The obtained concentrate was dissolved in chloroform, and the chloroform solution was chromatographed on 150 g of florisil with Aug. (1-12%) of methanol alcohol as eluent. The dark layer chromatography method found the fractions to contain trans-DL-yl-propyl-S-ethoxyikairtoonyl-G-lketoideicahydroquinoline. 1, where R = n ^ CaH7 and R1 = COOC2H5 / IR spectrum / CHay 1715 -cm-1 ketone C = 0 17 and 25 cm-1 ester G = 0 NMR spectrum '/ GOdJ / \ W JYEHz /. 53 cycles / s, triplet, N ^ CH2 ^ CH2 — CH3 77 cycles / ls, triplet, —O — CH2 — CH3 250 cycles / s, k wartet, —O, CH2 —- CH3 2. Oxidation of the hydroxyl group with the reagent • Saretta (pyridine hydrochloride and chromol trioxide) yields the corresponding new 6-keto compound of Formula 1. Compounds of Formula 1 are intermediates for the preparation of new octanyldirazole [ 3,4 mg of quinolines, which are useful as dopamine agonists. A mixture of 10 ml of propylamphine and 400 ml of toluene was cooled in a mixture of lyodine water. A solution of 16.5 g of ethyl α-bromomethyl acrylate was added dropwise thereto. The resulting mixture was stirred and cooled for about 25 minutes. A solution of 11 g of 4-lhenzoyloxycyclohe'xanone in 75 ml of toluene was then added dropwise to it. This new mixture was refluxed under nitrogen for 213 hours. The reflux coolers were equipped with a Soxlet extraction cap filled with 5A molecular sieves to remove the water. ¦Naistejpinlie the reaction mixture was chilled and filtered. In the remainder (after the removal of the solvents, there was 1-propyl-3-ethoxyloxy-bonyl-6-benzoyloxy-1,2,3,4,5,6,7,8K) k) tahydTochmoline ora-z. : opyl-3-ethoxycairibonyl-6-ibenzoyloxy-yl, 2 (3,4,4a, i5,6,7-olctahydroquinoline. This residue was dissolved in a mixture of ether-chloroform and the resulting solution. saturated with hydrogen chloride gas while maintaining the reaction temperature in the range of 0-5 ° C. The solvent was decanted from the crystals of the hydrochloride thus obtained. The hydrochloride was dissolved in 100 ml of methanol, 300 ml of THF was added and the final solution of the solution was dissolved with ice and water mixed with ice. During the mixing and cooling, 15 g of sodium hydrate were then added in portions, the reaction mixture was then mixed loosely and further diluted with sodium carbonate void solution. Alkaline water. the mixture was extracted several more times with ethyl acetate, the extracts were drained and washed with saturated water. . aqueous sodium chloride solution and dried. After the solvent had been stripped off, the trans-DLnl-petroleum-G2O-lrarbonylor -lbenizoylphs were obtained. This compound was dissolved in 400 ml of methanol and 100 ml of 2N aqueous solution of sodium hydroxide and stirred at temperature. in a room under a nitrogen atmosphere in. After this time, the volatiles were removed by evaporation under vacuum. The resulting residue was dispersed in 800 ml of ethanols and 1.5 ml of 1 2N aqueous acid, juice. ; The esterification mixture was heated to reflux under a chiller. dizzy and distilled off about 300 ml of solvent. Then a further 300 ml of ethanofl was added and the reaction mixture was refluxed for 26 hours in an apparatus equipped with a PL PL

Claims (2)

1. Zastrzezenia patentowe 1.. Sposób wytwarzania nowych 6-ketodlekahy- drochinolin o ogóllnym wzomze 1, w którym R o- znacza grupe alkilowa o 1—3 atomach wegla, gru¬ pe alljilowa lufo grupe benzylowa a R1 oznacza grupe o wzorze OOOZ', gdzie Z' oznacza grupe etylowa, znamienny tym, ze. zwiazek o .ogóHnym wzorze 2, w którym R i Z^maija wyzej podane . znaczenie, poddaje sie reakcjd z chlorowodorkiem pirydyny i trójtlenkiem chromu.1. Claims 1. A method for the preparation of the new 6-keto-hydroxyhydroquinolines of the general formula I, in which R is an alkyl group of 1-3 carbon atoms, an alloyl group or a benzyl group and R1 is a group of formula OOOZ ' where Z 'is an ethyl group, characterized in that. a compound of the general formula II, in which R and Z are as given above. meaning, it is reacted with pyridine hydrochloride and chromium trioxide. 2. Sposób wytwarzania nowych 6-ketodekiahy- ójrochinolin o ogólnym wzorze 1, w którym R o- znacza grupe alkilowa o 1—3 atoiraach wegla, gru¬ pe allilowa lub grupe benzylowa a R1 oznacza grupe o wzorze COOZ', gdzie Z' oznacza .grupie metylowa lub grupe alkilowa o 1—/2 atomach we^ gla poidistawioina girupa fenylowa, znajmieminy tym, ze zwiazek o ogólnym wzorze 2, w którym R i Z' maja wyizej podane znaczenie, ,poddaije Sie reakcji z chlorowodorkiem pirydyny i tróijtlenlkiem chro¬ mu, 10 15 20 25 30 35 40 45 50 55 •120 037 o RNH, Wzór 3 o-co-z HC^S^COOZ' Wzór 2 l N CH2=C-COOZ' CH2 Hal _0H" JtpJH HCl pirydyna • HCl Cr03 °€DCWZ' R Wzór 1 Schemat 7 Wzór 4 _ CO K COOZ' kwasBH; Wzór 5 & Wzór 1 HO- H R COOZ' PL PL2. Process for the preparation of the new 6-ketodeciahydroquinolines of the general formula I, in which R is an alkyl group of 1-3 carbon atoms, an allyl group or a benzyl group, and R1 is a group of the formula COOZ ', where Z' is a methyl group or an alkyl group of 1-2 carbon atoms. ¬ mu, 10 15 20 25 30 35 40 45 50 55 • 120 037 o RNH, Formula 3 o-co-z HC ^ S ^ COOZ 'Formula 2 l N CH2 = C-COOZ' CH2 Hal _0H "JtpJH HCl pyridine • HCl Cr03 ° € DCWZ 'R Formula 1 Scheme 7 Formula 4 _ CO K COOZ' acidBH; Formula 5 & Formula 1 HO- H R COOZ 'PL EN
PL1979225532A 1979-01-22 1979-06-29 Process for preparing novel 6-ketodecahydroquinolines PL120037B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US506179A 1979-01-22 1979-01-22
US06/031,641 US4198415A (en) 1979-01-22 1979-04-19 Prolactin inhibiting octahydro pyrazolo[3,4-g]quinolines

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PL1979225532A PL120037B1 (en) 1979-01-22 1979-06-29 Process for preparing novel 6-ketodecahydroquinolines
PL1979225533A PL119785B1 (en) 1979-01-22 1979-06-29 Method of manufacture of novel 6-hydroxydecahydroquinolines
PL1979225531A PL119715B1 (en) 1979-01-22 1979-06-29 Process for preparing novel 6-keto-7-dimethylaminomethylen-decahydroquinolinesekagidrokhinolinov
PL1979216719A PL122153B1 (en) 1979-01-22 1979-06-29 Process for preparing novel octahydropyrazolo-/3,4-g/ quinolinesnov

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PL1979225533A PL119785B1 (en) 1979-01-22 1979-06-29 Method of manufacture of novel 6-hydroxydecahydroquinolines
PL1979225531A PL119715B1 (en) 1979-01-22 1979-06-29 Process for preparing novel 6-keto-7-dimethylaminomethylen-decahydroquinolinesekagidrokhinolinov
PL1979216719A PL122153B1 (en) 1979-01-22 1979-06-29 Process for preparing novel octahydropyrazolo-/3,4-g/ quinolinesnov

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